Theoretical insights into nitrogen oxide activation on halogen defect-rich {001} facets of bismuth oxyhalide

doi:10.1016/j.jmst.2020.10.008

Abstract

Abstract:

Surface vacancies, serving as the activation centers for surface-adsorbed species, have been widely applied in catalysts to improve their activity and selectivity. In the case of ternary compound semiconductors, there is some controversy about exposed atoms and surface defects. Two-dimensional layered BiOCl is an important photocatalyst, which has had numerous studies focused on its oxygen vacancy (O_V) and bismuth vacancy (Bi_V). It has been realized that its (001) surface can consist of exposed halogen atoms rather than oxygen atoms, which thus needs a new explanation for its surface defect engineering mechanism. Using first-principles calculations, the activation behavior of NO_X (NO₂, NO, N₂O) at a chlorine vacancy (Cl_V) on the BiOCl (001) surface is systematically studied. It is found that after introducing Cl_V on BiOCl (001) surfaces, NO_X molecules all show excellent activities with longer chemical bonds by capturing electrons from the catalyst. Our work furnishes fundamental insight into the activation of small molecules on defect-rich surfaces of ternary compound catalysts.

Key words: BiOCl, Surface chlorine vacancy, NO_X(NO₂NON₂O) molecules, Selective reduction

Kang Xu, Liang Wang, Haifeng Feng, Zhongfei Xu, Jincheng Zhuang, Yi Du, Feng Pan, Weichang Hao. Theoretical insights into nitrogen oxide activation on halogen defect-rich {001} facets of bismuth oxyhalide[J]. J. Mater. Sci. Technol., 2021, 77: 217-222.

Figures/Tables 6

Fig. 1. (a) Surface energy and (b) defect formation energy of BiV, OV, and ClV on Cl-B001 facetes. The Cl-terminated surface Cl1-Cl2 has the lowest surface energy, indicating the most likely exposure of the BiOCl (001) surface. Under this exposure, the surface Cl vacancy has the lowest formation energy.

Fig. 2. Density of states of (a) Cl-B001 (b) Clv-Cl-B001, and the band decomposed charge density of (c) the VBM of perfect Cl-B001, (d) the CBM of perfect Cl-B001, and (e) the VBM of Clv-Cl-B001. (f) The surface vacancy state (SVS) of Clv-Cl-B001. The Fermi level is set at zero in (a) and (b). The isosurface of the charge density corresponds to 0.0025 e/? in (c)-(f).

Table 1. The adsorption energy, bond lengths, and bond angles of adsorbed and isolated NOX molecules. Eads is the adsorption energy. L(N1-O1), L(N1-O2), and L(N1-N2) are the bond lengths of NOX. θ is the angle of the molecule. Adsorbed and isolated represent the positions of molecules that are adsorbed on ClV-Cl-B001 and free, respectively.

	E_ads(eV)	L_(N1-O1)(Å)	L_(N1-O2)(Å)	L_(N1-O1/O2)(Å)	L_(N1-N2)(Å)	L_(N1-N2)(Å)	θ (°)	θ(°)
		adsorbed	adsorbed	isolated	adsorbed	isolated	adsorbed	isolated
NO₂-1	-2.8	1.37	1.21	1.21	-	-	113.32	133.83
NO₂-2	-2.89	1.34	1.23		-	-	112.99
NO₂-3	-2.39	1.27	1.27		-	-	116.9
NO₂-4	-2.61	1.27	1.27		-	-	115.99
NO₂-5	-2.65	1.27	1.27		-	-	114.74
NO₂-6	-2.76	1.27	1.27		-	-	115.58
NO₂-7	-2.65	1.27	1.27		-	-	115.06
NO₂-8	-2.68	1.26	1.26		-	-	114.45
NO-1	-1.74	1.24	-	1.17	-	-	180	180
NO-2	-1.21	1.29	-		-	-
NO-3	-1.78	1.25	-		-	-
NO-4	-1.74	1.23	-		-	-
N₂O-1	-0.58	1.19	-	1.2	1.15	1.14	180	180
N₂O-2	-0.59	1.22	-		1.14		180
N₂O-3	-0.49	1.32	-		1.19		132.73
N₂O-4	-1.57	-	-		1.11		-

Fig. 3. Adsorption energy, crystal structure and charge density difference for the adsorbed configurations NO2-1, NO2-2, NO-2, NO-3, N2O-3, and N2O-4 which have lowest adsorption or highest activation of NO bonds. Yellow and blue colors represent the gain and loss of electrons, respectively. The bond lengthes of N-O in free NO2, NO and N2O are 1.21 ?, 1.17 ? and 1.20 ? and N-N distance in free N2O is 1.14 ?.

Table 2. Charge transfer analysis of Bi1, Bi2, Bi3, and Bi4 around ClV and O1, O2, N1, and N2 of NOX. Here, we give the electron acceptors (+) and donors (-) compared with the ClV-Cl-B001 or isolated NOX to analyze the charge transfer before and after NOX adsorption on ClV-Cl-B001.

	Bi1	Bi2	Bi3	Bi4	O1	O2	N1	N2
NO₂-1	-0.0828	-0.0828	-0.078	-0.078	0.4491	0.1373	0.1595	—
NO₂-2	-0.0722	-0.0723	-0.0909	-0.076	0.3931	0.1578	0.1874	—
NO₂-3	-0.0886	-0.0886	-0.0886	-0.0886	0.2014	0.2024	0.386	—
NO₂-4	-0.103	-0.0639	-0.0641	-0.1029	0.2087	0.2092	0.3456	—
NO₂-5	-0.0962	-0.0962	-0.0963	-0.0963	0.3118	0.3105	0.1663	—
NO₂-6	-0.1136	-0.0628	-0.0628	-0.1136	0.3015	0.3017	0.171	—
NO₂-7	-0.0937	-0.0921	-0.0938	-0.0921	0.3054	0.3058	0.1624	—
NO₂-8	-0.1088	-0.0705	-0.0739	-0.1089	0.2303	0.2298	0.2874	—
NO-1	-0.0492	-0.0492	-0.0492	-0.0492	-0.0569	—	0.6691	—
NO-2	-0.0719	-0.0719	-0.0722	-0.0722	0.2451	—	0.4902	—
NO-3	-0.0855	-0.0855	-0.0854	-0.0854	0.0366	—	0.6541	—
NO-4	-0.0488	-0.0492	-0.0504	-0.0443	-0.0608	—	0.6719	—
N₂O-1	-0.0194	-0.0194	-0.0194	-0.0194	-0.1483	—	0.1584	0.0038
N₂O-2	-0.0197	-0.0197	-0.0197	-0.0197	0.1254	—	0.4139	-0.5214
N₂O-3	-0.0941	-0.0941	-0.0764	-0.0764	0.3141	—	0.1698	0.2471
N₂O-4	-0.0874	-0.0793	-0.0797	-0.072	0.4503	—	0.286	0.0351

Fig. 4. Density of states of adsorbed molecules of NOX, and the 4Bi atoms and 4Cl atoms that are the nearest neighbors and next nearest neighbors of ClV in the adsorbed configurations: (a) NO2-1, NO2-2, (b) NO-2, NO-3, and (c) N2O-3, N2O-4, which has the lowest adsorption energies or highest activation of N—O bonds. NO2-1, NO2-2, NO-2, NO-3 and N2O-4 show strong interactions with ClV-Cl-B001.

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